Process for precipitating artificial threads, ribbons, films, and the like of viscose



Patented Jan. ll, i927.

ADOLF KKMPF, or PREMNITZ, GERMANY.

PROCESS FOR PRECIPITATING ARTIFICIAL THREADS, RIBBONS, FILMS, AND THELIKE OF VISGOSE.

N Drawing. Application filed January 27, 1926, Serial No. 84,174. and inGermany August 6, 1921.

The present invention relates to the manufacture of artificial threads,ribbons, films and the like, and more particularly to products of suchcharacter made from viscose.

5 The present application is a continuation in part of a 'copendingapplication Serial No. 57 9,301, filed August 2, 1922.

The chief object of the invention is to provide a new and improvedspinning bath for use in such manufacture.

t-her objects will be explained hereinafter and will be pointed out inthe appended claims. 1

' It is now well known that wood and other [5 cellulose-containingsubstances may be disintegrated by means of phenols to produce asulphonated resinous condensation product of the wood and the phenol. Adescription of the method .may be found, for example, in German PatentNo. 247,181 to Mauthner. The following steps have been found veryserviceable: 100 to 150 kilograms melted phenol and 3 kilogramsconcentrated sulphuric acid (preferably about 96%) are mixed with 50 to60 kilograms sawdust and heated for about ten minutes at a temperatureof about 40 to 50 degrees. The sawdust should be dry, though it maycontain about ten per cent moisture. During the heating, the mixture isslowly stirred. Va-

forming substances, or substances of an aciduous or acidlfylng charactermay be used'as catalyzers durmg the heating. A brownish- 3 the heatrenders very fluid. This product is stirred and 5 liters concentratedsulphuric acid is added. This'acid' may itself be the catalyzer. Thetemperature should be kept down to 100 or 105 degrees. At intervals ofabout four minutes, concentrated sulphuric acid is added in similarfashion in about five-liter quantities until a total quantity of about198 liters has been added. After about an hour, an aqueous sulphuricacidsolution of the resinous, phenol-wood condensation product willbeproduced that is soluble in water. The wood may be more or lessdisintegrated, as desired.

According to the present invention, this sulphonated resin isconcentrated to the de-' sired degree, and then added. to sulphuric acidin about the proportions of 10 to 12 per Other and furrious organic orinorganic acids or acid-' black,tar-like resinous product results whichcent acid to about 5 per cent of the phenol-wood-sulphuric-acid reactionproduct.

About 15 per cent sulphate of sodium is also contained. A very valuablespinning bath is thus produced. Under a normal drawingoif speed of .5meters to the minute, the length of the bath may be about centimeters.The temperature of the bath, using wholly unripe viscose, may be 18degrees.

The resulting threads are of especially good physical structure, beingvery firm, with correspondingly valuable properties,

including a beautiful lustre. The firmness is greater than thatobtainable with priorart salt baths, to which sulphuric acid is added.This is especially the case when the viscose used in wholly unripe, madefrom alkali cellulose that has not ripened completely, though goodresults are obtained also with fresh viscose from ripe alkali cellulose.

The condensation products produced as above described containconsiderable quantieies of sulphuric acid. It may be used in this verycondition, dissolved in Water or dilute sulphuric acid, forspinning-bath amount of concentrated sulphuric acid added to about 90kilograms. The result will be a product containing little or no mineralacid. Such free sulphuric acid as still ex I ists may be neutralized byadding alkalies, like caustic soda or sodium carbonate. Or, aproportionately weaker acid bath may be used, adding to the bathsuitable proportions of salts of the mineral acid or of the resinoussulphuric acid in question to the same. The quantity of salts added willdepend upon the purpose sought to be attained. Salts soluble in watermay also be added to the sulphuric or mineral acids.

' Soluble glue-precipitating sulphonic aclds of mineral oils, soluble.in water, aliphatic tars or tar oil, for instance, portions ofsowaterthat are able to precipitate the called acid resin soluble in Water, areparticularly well suited for precipitating viscose solutions. Thesemaybe used with or without additions of acids or salts. As anillustration of a soluble, glue-precipitating sulphuric acid of amineral oil, machine oil, of specific gravity 0.929, viscosity 5,Engler' degrees at 50 degrees, flash point 182 degrees, and burningpoint 212 degrees is sulphonated at roomtemperature, in any well knownWay, with sulphonic acid monhydrate.

The prccipitating bath, for instance, may contain, in addition tosulphuric acid and 5-1 0% sodium sulphate, 6% lignite tar sulphonicacid. With this bath, and using viscose obtained without any artificialripening, very solid fibres of high lustre are obtained.

Other aromatic sulphonic acids soluble in glue solution may also beused. Among other substances suitable for this purpose are: aromaticsulphonic acids Whichprecipitate glue, products of condensation ofsulphonic acids with aldehydes or ketones, and products of condensationobtainable by heating homogeneous or mixed aromatic sulphonic acids,alone or together with substances having an aflinity for Water. Forexample, the bath may contain a soluble aromatic sulphonic acid adaptedto precipitate a glue solution and a condensation prod not of sulphonicacid of naphthalene and formaldehyde. Reference maybe made to BritishPatent No. 116,935 of 1918, and to- German Patent No. 262,556 toStriasny, both ofwhich disclose a glue-precipitating, aromaticsulphonicacid. Isopropyl sulphonic acid may be added. Another such condensationproduct is disclosed in German Patent No; 292,531. The most variedproducts may be used, irrespective'of Whether they be viscose threadswill be of the very greatest fineness. The temperature of the bath maybe degrees C., the dragging length about 40 cins. and the drawing-offspeed 43 meters a minute. The threads have high lustre and solidity.

It is to be.understood that the invention is not limited to the exactembodiments thereof.

disclosed herein, but that modifications may bath may consist of be madeby persons skilled in the art- Without de'parting'from its spirit andscope.

What is claimed is:

1. A. method of producing artificial threads, films,ribbons and the likethat comprises precipitating viscose in an aqueous solutionof asulphonic acid of the condensation product obtained .by'disintegrating acellulose-containing substance bv means of phenols.

2. A method of producing artificial threads, films, ribbons and the likethat comprises precipitating viscose in an aqueous solution of asulphonic acid of the condensation product obtained by disintegrating acellulose-containing substance by means of phenols. the said aqueoussolution, containing a mineral salt.

3. A method of producing artificial threads, films, ribbons and the likethat comprises precipitating viscose in an aqueous solution of asulphonic acid of the condensation product obtained by disintegrating acellulose-containing substance by means of phenols, thesaid aqueoussolution containing a salt soluble in water.

L A method of producing artificial threads, films, ribbons and the Iikethat comprises precipitating unripened viscose in an aqueous solution ofa sulphonic acid of the condensation product obtained'by disintegratinga cellulose-containing substance byv means of phenols, the said aqueoussolution containing mineral salts and salts soluble threads, films,ribbons' and the like that tomprises precipitating viscose in an,aqueous solution ofa sulphonic acid-. of the condensation productobtained: by dlsintegrating a cellulose-containing; substance by meansof phenols, the said aqueous solution containmg a Solubleglue-precipitating sulphonic acid of a mineral oil.

6. A method of producing artificial threads, films, ribbons andthe'li'ke that comprises precipitating viscose in an aqueous so lutionof asulphonic acid of the condensation product obtained bydisintegrating a cellulose-containing substance by means of phenols, thesaid aqueous solution containing a soluble aromatic sulphonic acidadapted to precipitate a glue solution.

7. A method of producing artificial threads, films, ribbons and the likethat comprises precipitating viscose in an aqueous solution of asulphonic acid of the condensation product obtained by disintegrating acelluloseecontainirig substance by meansTof phenols, the saidaqueoussolution containing a soluble aromatic sulphonicacid adapted toprecipitate a glue solution and a condensation product of sulphonic acidof naphthalene and formaldehyde.

8. A method of producing artificial prises precipitating viscose in anaqueous solution of a sulphonic acid of the condensation productobtained by disintegrating a 5 cellulose-containing substance by'meansof phenols,- the said aqueous solution containing a solubleglue-precipitating sulphonlc acid of almineral oil, aliphatic tar or taroil, a soluble aromatic sulphonic acid adapted to precipitate a gluesolution and a precipi- 10 tating-furthering product.

In testimony whereof, I have hereunto subscribed my-name.

DR. ADOLF KKMPF.

